Chemistry is being developed for an efficient synthesis of daunomycinone, adriamycinone, and related aglycones. Special emphasis is being placed on a route which will allow preparation of optically active, 14C-ring labeled anthracyclines for tissue distribution and metabolism studies. Results thus far have afforded an efficient synthesis of plus or minus 7-deoxydaunomycinone. Work currently in progress has focused on an efficient conversion of the latter compound to daunomycinone and adriamycinone, resolution of the anthracyclinones and an efficient synthesis of 14C-labeled 3-methoxydimethylphthalate. A parellel study involves a short synthesis of the rhodomycinone and alkavinone anthracyclinones via functionalized naphthalene derivatives. These studies have involved a novel electrochemical synthesis of methoxyjuglone and its regiospecific functionalization to a common precursor to both the rhodomycinone and alkavinone ring systems. Finally, work in conjunction with other investigators will involve coupling of these syhthetic aglycones with fraudulent sugars to prepare a series of unnatural anthracycline antibiotics for antitumor testing.